CN110302592B - Back-blowing resistant nanofiber composite filter material and preparation method thereof - Google Patents
Back-blowing resistant nanofiber composite filter material and preparation method thereof Download PDFInfo
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/02—Loose filtering material, e.g. loose fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/02—Loose filtering material, e.g. loose fibres
- B01D39/04—Organic material, e.g. cellulose, cotton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/30—Particle separators, e.g. dust precipitators, using loose filtering material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/02—Types of fibres, filaments or particles, self-supporting or supported materials
- B01D2239/0241—Types of fibres, filaments or particles, self-supporting or supported materials comprising electrically conductive fibres or particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0471—Surface coating material
- B01D2239/0492—Surface coating material on fibres
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nonwoven Fabrics (AREA)
- Filtering Materials (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The invention discloses a preparation method of a blowback-resistant nanofiber composite filter material, which comprises the following steps: providing a fiber base material, wherein conductive powder is added into the base material in the preparation process to form a static dissipative material; and depositing a nanofiber layer on at least one surface of the fiber base material by using an electrostatic spinning polymer solution method to obtain the composite filter material. The invention also provides the blowback-resistant nanofiber composite filter material prepared by the method. The preparation method provided by the invention has the advantages of one-step molding, simple process, low production cost and excellent back-blowing resistance of the obtained composite filter material.
Description
Technical Field
The invention relates to the field of filter materials, in particular to a blowback-resistant nanofiber composite filter material and a preparation method thereof.
Background
The air pollution problem is concerned nowadays, and the world advocates environment-friendly, efficient and environment-friendly energy utilization. The gas turbine air inlet system and the industrial dedusting system continuously put forward higher standard requirements on the technical indexes of the filtering base material from the aspects of filtering efficiency, resistance pressure drop, dust holding capacity and service life. The nano-scale fiber net air filter material prepared by high-pressure electrostatic spinning has the characteristics of high efficiency and low resistance. Compared with the nanofiber composite air filter material and the deep-layer air filter material, the nanofiber composite air filter material has the advantages that the filtration mechanism of the nanofiber composite air filter material is mainly surface mechanical interception, most particles are captured and accumulated on the surface of the filter material, the particles can be recycled through dynamic pulse back blowing purification, and if the technical index of back blowing resistance can be achieved, the nanofiber composite air filter material has higher dust holding capacity and longer service life in actual use.
The high-voltage electrostatic spinning nanofiber composite filter material is one of the best filter materials of an industrial dedusting air system of a gas turbine air inlet system. Donaldson, Finetex Mats are among others for realizing industrial mass production by international technological breakthroughTM，AntimicrobeWebTM，NanoFilterTM，Fibra-WebTMA brand merchant. After investigation, the defects that the nano fiber net falls off from the base material in different degrees appear in the whole-life pulse back-blowing airflow cleaning process except Donanldson, so that the filtering efficiency and the dust holding capacity are continuously reduced after the circulation back-blowing, the operation time of the filter is seriously shortened, and the use cost is increased.
The filter material technology in China is relatively laggard, the market from military (052 series ships and 055 series ships) to the high-end filter core filter material (F9 grade standard EN779-2012) of the gas turbine air inlet system of a civil power plant is monopolized by foreign countries (Donanldson), the technology of high-pressure electrostatic spinning nano-fiber is mostly stopped at the laboratory stage according to research of enterprises and technical schools in China, and the nano-fiber composite filter material from equipment to process mass production also has many technical problems to be broken through. Such as: the CN101940856A and CN102908829A patents do not consider the technical index of full-life pulse back-blowing cleaning in the preparation, so that the breakage of the nanofiber web surface is easily caused, and the product cannot provide stable and high-quality air for the gas turbine under the condition of dynamic pulse back-blowing. The technical scheme of using solvent steam to cause adhesion between fibers in the patent CN104028047B has a safety problem, and the method for realizing wear resistance and peeling resistance has great potential safety hazard. It is known that the working voltage in the mass production process of high-voltage electrostatic spinning is often as high as tens of thousands of volts, and the control of the concentration of solvent vapor in the high-voltage field intensity is a prerequisite condition for safe mass production. The prior art patents have the characteristics of high difficulty in industrial mass production, complex production procedures and high production cost.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a blowback-resistant nanofiber composite filter material, the preparation method is formed at one time, the process is simple, the production cost is low, and the obtained composite filter material has excellent blowback-resistant performance.
The invention aims to provide a preparation method of a blowback-resistant nanofiber composite filter material, which comprises the following steps:
providing a fiber base material, wherein conductive powder is added into the base material in the preparation process to form a static dissipative material; and
and depositing a nanofiber layer on at least one surface of the fiber base material by using an electrostatic spinning polymer solution method to obtain the composite filter material.
Further, the minimum filtration efficiency of the composite filter material is 60%.
Further, the base material is a filter paper base material prepared by wet papermaking technology or a non-woven fabric base material prepared by a melt-blowing method. Further, the weight of the filter paper base material is 20-140 gsm, and the weight of the non-woven fabric base material is 20-250 gsm.
Further, the raw materials of the filter paper substrate comprise the following components in parts by mass: 10-19.5% of reinforcing fibers, 5-7% of conductive powder and the balance of wood pulp fibers.
Further, the reinforcing fibers are selected from PET fibers and/or PP fibers, the diameter of the reinforcing fibers is preferably 50-70 mu m, the length of the reinforcing fibers is preferably 5-10 cm, and the reinforcing fibers can increase the stiffness, the rupture strength and the weather resistance of the fiber base material.
Further, the raw materials of the non-woven fabric base material comprise the following components in parts by mass: 5-7% of conductive powder and the balance of a polymer, wherein the polymer is at least one selected from polyester fiber (PET), polypropylene, polyvinylidene fluoride, PA6 and PA 66.
Further, the conductive powder is at least one selected from the group consisting of metal conductive powder, metal oxide conductive powder and carbon conductive powder, and the particle size of the conductive powder is 50 to 6000nm, preferably 50 to 300 nm. The metal conductive powder comprises silver powder, aluminum powder and copper powder; the metal oxide conductive powder comprises antimony-doped tin dioxide, aluminum-doped zinc oxide and indium-doped tin oxide; the carbon-based conductive powder comprises carbon fiber powder, conductive carbon black, carbon nanotubes and graphene. The preferred conductive powder is carbon fiber powder, which has good conductivity, ductility and dispersibility, and low cost.
Further, the polymer in the polymer solution is selected from at least one of the following materials: polyvinylidene fluoride, polyurethane, polyacrylonitrile, polymethyl methacrylate, polylactic acid, polyamide, polyimide, polyaramide, polybenzimidazole, polyethylene terephthalate, polypropylene, polyaniline, polyethylene oxide, polyethylene naphthalate, polybutylene terephthalate, styrene-butadiene rubber, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyvinyl butene, and copolymers or derivatives thereof.
Further, the polymer solution is formed by mixing a polyvinylidene fluoride solution and a polyurethane solution in a mass ratio of 9: 1-5: 5; the polyvinylidene fluoride solution is prepared from polyvinylidene fluoride and a mixed solvent in a mass ratio of 1: 9-20, and the polyurethane solution is prepared from polyurethane and the mixed solvent in a mass ratio of 1: 9-15; the mixed solvent comprises a solvent A and a solvent B in a mass ratio of 9: 1-5: 5, wherein the solvent A is N, N-dimethylformamide or N, N-dimethylacetamide, and the solvent B is acetone or butanone. The electrostatic spinning nanofiber prepared from the polymer solution integrates the advantages of two materials, shows the characteristics of high strength, good toughness, wear resistance, cold resistance, oil resistance, water resistance, aging resistance, weather resistance and the like, and has the characteristics of high waterproofness, bacteria resistance, mildew resistance and ultraviolet resistance.
Further, the polymer solution contains 0.01-0.5 wt% of a conductive aid to increase the conductivity of the polymer spinning solution. Preferably, the conductive aid is tetrabutylammonium perchlorate.
The invention also provides the blowback-resistant nanofiber composite filter material prepared by the method.
The principle of the invention is as follows: in the invention, the surface resistance of the base material fiber is 10 by adding the conductive powder into the base material fiber4～1011Omega, the fiber is used as a static dissipative material, so that static charges on the surface of the fiber can be conducted and dissipated in time. When the substrate receives the electrostatic spinning nano-fiber, the charges on the nano-fiber falling on the substrate fiber are dissipated and disappeared quickly due to no aggregation condition, and the charges on the surface of the nano-fiber falling in the pores of the substrate fiber are enriched continuously, so that the nano-fiber among the pores of the substrate fiber is electret, and finally generates a potential difference with the nano-fiber on the substrate fiber. Under the action of electrostatic force, the falling point of the high-voltage electrostatic spinning nanofiber tends to the substrate fiber, and finally, the irregular greens rich in nanofibers are formed on the substrate (as shown in figures 3 and 4).
The invention has the beneficial effects that:
1. according to the invention, the conductive functional powder is added in the preparation process of the substrate, so that the prepared substrate becomes an electrostatic dissipation material, the distribution trend of the electrostatic spinning nano-fibers is effectively controlled by adjusting the electrostatic resistivity of the substrate fibers, and the contact area of the nano-fibers and the substrate fibers is increased under the condition of not obviously increasing resistance pressure drop, so that the adhesion of the nano-fibers and the substrate is enhanced, and the back-blowing resistance is improved.
2. The nanofiber composite filter material produced by the invention is formed at one time, and has the advantages of simple process, low production cost and excellent product performance. On F6-F8 grade (EN779-2012 standard) filter paper prepared by synthesizing wood pulp fibers and chemical fibers, the filtration efficiency is stabilized to F9(EN779-2012 standard) and above by electrostatically spraying nano fibers. The back-flushing resistance performance is perfect, and the dust holding capacity, the pulse back-flushing resistance and the comprehensive performance of the filter effect are tested to reach the standard of international high-end air filter materials.
Drawings
FIG. 1 is a schematic view of a single set of high voltage electrospinning apparatuses used in examples and comparative examples;
FIG. 2 is an electron microscope cross-sectional view of the composite filter prepared in example 3, wherein 201 is a nanofiber web layer and 202 is a substrate layer;
FIG. 3 is an electron microscope image of the green of nanofibers in the composite filter prepared in example 3;
FIG. 4 is an electron microscope image of the distribution of nanofibers in the composite filter prepared in example 3, wherein 401 is a nanofiber-rich region (nanofiber putting green) distributed on the fibers of the substrate, and 402 is a nanofiber-sparse region distributed in the voids of the substrate;
FIG. 5 is a Phenom fiber metric plot of nanofibers in the composite filter prepared in comparative example 3;
FIG. 6 is a Phenom fiber metric plot of the nanofibers in the composite filter prepared in example 3;
FIG. 7 is a surface topography after the composite nanofiber filter of example 3(a) and comparative example 1(b) is subjected to back blowing (@6kg @1000 times);
fig. 8 is a national grid test report.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
1. Raw materials
Polyurethane, lubrizol Estane TPU X595A-11 or Bayer TUP 9395 AU;
polyvinylidene fluoride, ARKEMA, france Kynar PVDF 761A;
ostone SY5043AD CW substrate: filtration efficiency F7, mass 118gsm, thickness 0.29, air permeability 193L @200Pa L/m2(s), average pore size 42.1 μm, filtration efficiency 50. + -. 5% @0.3 μm DEHS @ 32L;
RC-T380 carbon fiber powder produced by Innovative materials science and technology Limited of Liancheng, Lianchong, Jiangsu province, with a density of 1.77g/cm3Elongation 1.52%, carbon content 95.8%, ash 0.27%, water content 0.5%, particle size 4um, modulus 235Gpa, strength 4950Mpa, and conductivity 1.2 x 10-3。
2. Production equipment
The embodiment of the invention uses an industrialized production line to prepare 8 groups of spinning systems (the spinning needles are arranged upwards) for high-pressure electrospinning, wherein the industrialized high-pressure electrospinning production line is shown in figure 1, and at least the following equipment needs to be configured: unwinding unit 1, coiling mechanism 2, spout a room frame 3, receive screen 4, high voltage direct current power supply 5, spinning jet 6 spouts a group 7, spouts a group support 8, conveyer belt 9, transfer roller 10. The structure of the spinning nozzle and the spinning unit is described in detail in CN201811180346.9 patent, and the industrial batching system and the liquid supply system matched with the industrial high-voltage electrostatic spinning assembly line are described in CN 105019042B patent, which are not described in detail herein. The spinning unit is a modular component, and can be assembled by multiples of 4 according to the output requirement: 4, 8, 16 or more.
3. Detection device
The invention uses the following instruments: the tester comprises a TEXTEST FX3300 air permeability tester, a Phenom Pro electron microscope, a Phenom fiber metric system, a TSI 8130A filtration efficiency tester, a Boyu 8100 pulse back-blowing test bench and a FRASER 730SRM surface resistance tester.
Examples 1 to 4: preparation of back-blowing-resistant nanofiber composite filter material
(1) Preparation of Filter paper substrate
According to the proportion in table 1, the wood pulp fiber, the reinforcing fiber and the conductive powder are prepared into mixed slurry, and the mixed slurry is manufactured by a wet papermaking technology to prepare the filter paper substrate. The resulting filter paper substrate had a weight of 110gsm and a permeability of 250L @200Pal/m2(s) an average pore size of 56 μm and a filtration efficiency of 30. + -. 5% @0.3 μm DEHS @ 32L.
TABLE 1 formulation of filter paper substrate
| Wood pulp fiber (wt%) | Reinforcing fiber (wt%) | Conductive powder (wt%) | |
| Example 1 | 80 | 17 | 3 |
| Example 2 | 80 | 15 | 5 |
| Example 3 | 80 | 13 | 7 |
| Example 4 | 80 | 11 | 9 |
(2) Preparation of nanofibers on filter paper substrates
Parameters of the mixed solution: solute material: the proportion of the polyvinylidene fluoride solution to the polyurethane solution is 7: 3. solid content of the solution: 9% by weight of conductive additive: 0.1% tetrabutylammonium perchlorate, solvent: 90.9% DMF/MEK8:2, viscosity: 220 +/-5 cP and the conductivity of 300 +/-5 mu S/cm.
The production environment is as follows: in a constant-temperature and constant-humidity workshop, the temperature is 25 +/-2 ℃, the relative humidity is 25 +/-5 percent, the enthalpy value is 37 +/-5 kJ, and the fresh air volume of a production line is 18000m3H, recovery air volume (exhaust air) 18100m3The pressure in the equipment is (2.5 +/-0.5) Pa, and the concentration of the solvent gas<(10±0.5)ppm。
Production parameters are as follows: the solution amount is 700g/h, the spinning height is 120mm, the spinneret displacement speed is 45mm/s, the displacement distance is 50mm, the spinning voltage is 60kv, and the vehicle speed is 8.8 m/min.
The preparation process comprises the following steps:
the filter paper base material prepared in the embodiment 1-4 enters a spinning production line provided with 8 groups of spinning assemblies through an unwinding device 1, the filter paper base material is proportioned and supplied with liquid through an industrialized proportioning system and a liquid supply system, under the action of a high-voltage electric field, a large amount of charges are enriched in a solution positioned at the top ends of thousands of spray heads to form electrostatic repulsive force, the problem that the solution surface tension and self viscoelasticity form electrified jet flow to quickly ascend and be drawn is overcome, the solvent extremely-speed volatile solution is solidified to form nano-grade fibers which are uniformly deposited on the base material, and finally, the ring is looped through a winding device 2 to obtain the composite filter material.
The parameters of the composite filters prepared in examples 1-4 are shown in Table 2:
TABLE 2 Performance parameters of the composite filters prepared in examples 1-4
By PhenomThe fiber metric system tests that the diameters of the nano fibers in the composite filter material of the embodiment 3 are concentrated at 249-331 nm, and the pores of the nano fiber net are concentrated at 1864nm2(see FIG. 6), average pore diameter 0 μm.
Comparative example 1
Parameters of the mixed solution: solute material: the proportion of the polyvinylidene fluoride solution to the polyurethane solution is 7: 3, solid content of the solution: 9% wt conductive aid: 0.1% tetrabutylammonium perchlorate, solvent: 90.9% DMF/MEK8:2, viscosity: 220 plus or minus 5cP and the conductivity of 300 plus or minus 5 mu S/cm;
the production environment is as follows: in a constant-temperature and constant-humidity workshop, the temperature is 25 +/-2 ℃, the relative humidity is 25 +/-5 percent, the enthalpy value is 37 +/-5 kJ, and the fresh air volume of a production line is 18000m3H, recovery air volume (exhaust air) 18100m3The pressure in the equipment is (2.5 +/-0.5) Pa, and the concentration of the solvent gas<(10±0.5)ppm。
Production parameters are as follows: the solution amount is 700g/h, the spinning height is 120mm, the spinneret displacement speed is 45mm/s, the displacement distance is 50mm, the spinning voltage is 60kv, and the vehicle speed is 10 m/min.
The Oslon SY5043AD CW substrate is used as a filter paper substrate, and the high-voltage electrostatic spinning nano-fiber is prepared on the substrate, and the preparation process is the same as that of the example 1.
The fiber diameters are concentrated at 270-396 nm measured by a Phenom fiber metric system, and the pores of the nanofiber net are concentrated at 2139nm2(see FIG. 5). The air permeability of the composite filter material measured by a TEXTEST FX3300 air permeability tester is 157L @200Pal/m2And s. The filtration efficiency of the composite filter material measured by a TSI 8130A filtration efficiency tester is 80 +/-5% @0.3 mu m DEHS @ 32L.
Pulse back-blow resistance test
The composite filter materials prepared in the examples 3 and 1 were respectively tested for their blowback resistance by using a Boyu 8100 pulse blowback test stand, with a blowback pressure of 3-6 kg and a blowback area of 50.24cm2The number of blowback was 1000 times, and the results are shown in Table 3.
TABLE 3 blowback resistance test results for comparative example 1 and example 3 samples
According to the pulse back-blowing resistant data in table 3, the composite filter material obtained by electrospinning the nano fibers on the Oslon SY5043AD CW substrate is found to have obviously reduced filtration efficiency under the condition that the pulse back-blowing air pressure is 4-5 kg; when the back-blowing air pressure is increased to 6kg, the filtration efficiency is reduced by about 30 percent. It can be seen from the electron microscope image of fig. 7 that the composite filter of comparative example 1 was severely damaged.
The composite filter material prepared in the embodiment 3 has excellent back-blowing resistance, the filtering efficiency is not reduced when the back-blowing air pressure is 3-5 kg, and the filtering efficiency is not obviously reduced when the back-blowing air pressure is increased to 6 kg. As can be seen from the electron microscope image of fig. 7, the surface of the composite filter was not damaged.
Referring to the national grid test report of fig. 8, the composite filter of example 3 does not exhibit significant resistance pressure drop when the filtration efficiency of F9(EN779-2012 standard) is achieved. This is because the composite filter of example 1 increases the contact area between the nanofibers and the substrate, and enhances the adhesion between the nanofiber web and the substrate, thereby achieving excellent blowback resistance.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (11)
1. A preparation method of a blowback-resistant nanofiber composite filter material is characterized by comprising the following steps:
providing a fiber base material, wherein conductive powder is added into the base material in the preparation process to ensure that the surface resistance of the base material fiber is 104 ~ 1011Omega, becomes the static dissipative material; and
and depositing a nanofiber layer on at least one surface of the fiber base material by using an electrostatic spinning polymer solution method to obtain the composite filter material.
2. The method of claim 1, wherein the substrate is a filter paper substrate made by wet paper making or a non-woven fabric substrate made by melt blowing.
3. The preparation method of the blowback-resistant nanofiber composite filter material as claimed in claim 2, wherein the raw materials of the filter paper substrate comprise the following components in parts by mass: 10-19.5% of reinforcing fibers, 5-7% of conductive powder and the balance of wood pulp fibers.
4. The preparation method of the blowback-resistant nanofiber composite filter material as claimed in claim 2, wherein the raw materials of the non-woven fabric substrate comprise the following components in parts by mass: 5-7% of conductive powder and the balance of polymer, wherein the polymer is at least one selected from PET, polypropylene, polyvinylidene fluoride, PA6 and PA 66.
5. The preparation method of the blowback-resistant nanofiber composite filter material as claimed in claim 3 or 4, wherein the conductive powder is at least one selected from a metal-based conductive powder, a metal oxide-based conductive powder and a carbon-based conductive powder, and the particle size of the conductive powder is 5 to 30 nm.
6. The preparation method of the blowback-resistant nanofiber composite filter material as claimed in claim 5, wherein the metal conductive powder comprises silver powder, aluminum powder and copper powder; the metal oxide conductive powder comprises antimony-doped tin dioxide, aluminum-doped zinc oxide and indium-doped tin oxide; the carbon-based conductive powder comprises carbon fiber powder, conductive carbon black, carbon nanotubes and graphene.
7. The preparation method of the blowback-resistant nanofiber composite filter material as claimed in claim 1, wherein the polymer in the polymer solution is selected from at least one of the following materials: polyvinylidene fluoride, polyurethane, polyacrylonitrile, polymethyl methacrylate, polylactic acid, polyamide, polyimide, polyaramide, polybenzimidazole, polyethylene terephthalate, polypropylene, polyaniline, polyethylene oxide, polyethylene naphthalate, polybutylene terephthalate, styrene-butadiene rubber, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyvinyl butene, and copolymers or derivatives thereof.
8. The preparation method of the blowback-resistant nanofiber composite filter material as claimed in claim 7, wherein the polymer solution is formed by mixing polyvinylidene fluoride solution and polyurethane solution in a mass ratio of 9: 1-5: 5;
the polyvinylidene fluoride solution is prepared from polyvinylidene fluoride and a mixed solvent in a mass ratio of 1: 9-20, and the polyurethane solution is prepared from polyurethane and the mixed solvent in a mass ratio of 1: 9-15;
the mixed solvent comprises a solvent A and a solvent B in a mass ratio of 9: 1-5: 5, wherein the solvent A is N, N-dimethylformamide or N, N-dimethylacetamide, and the solvent B is acetone or butanone.
9. The preparation method of the blowback-resistant nanofiber composite filter material as claimed in claim 1, wherein the polymer solution contains 0.01-0.5 wt% of conductive additive.
10. The preparation method of the blowback-resistant nanofiber composite filter material as claimed in claim 9, wherein the conductive additive is tetrabutylammonium perchlorate.
11. The blowback-resistant nanofiber composite filter material prepared by the method of any one of claims 1-10.
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| CN111282345A (en) * | 2020-02-24 | 2020-06-16 | 深圳维度新材料有限公司 | Preparation method of composite material layer, composite material layer and air purification filter material |
| CN111457525B (en) * | 2020-04-27 | 2021-12-10 | 安徽合众智信科技咨询有限公司 | Flexible composite fiber material for sterilizing and filtering fresh air system |
| KR102606295B1 (en) * | 2020-10-05 | 2023-11-27 | 주식회사 휴비스 | High Heat Resistant Multilayer Filter Media |
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| CN103877783B (en) * | 2014-04-10 | 2015-10-21 | 北京石油化工学院 | Preparation method of heatable sandwich type purification material |
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